3 years ago

Accessing Stable Magnesium Acyl Compounds: Reductive Cleavage of Esters by Magnesium(I) Dimers

Accessing Stable Magnesium Acyl Compounds: Reductive Cleavage of Esters by Magnesium(I) Dimers
Cameron Jones, Andreas Stasch, Carlos A. Lamsfus, Laurent Maron, Brant Maitland, Aaron J. Boutland
The first examples of magnesium acyls, [(Nacnac)Mg{μ-C(Ph)O}(μ-OR)Mg(Nacnac)] (R=Me, tBu or Ph; Nacnac=[HC(MeCNAr)2]−; Ar=C6H2Me3-2,4,6 (MesNacnac), C6H3Et2-2,6 (DepNacnac), C6H3iPr2-2,6 (DipNacnac)), have been prepared by reductive cleavage of a series of esters using dimeric magnesium(I) reducing agents, [{(Nacnac)Mg}2]. Crystallographic studies reveal the complexes to be dimeric, being bridged by both phenyl-acyl and alkoxide/aryloxide fragments. The crystal structures, combined with results of spectroscopic and computational studies suggest that the nature of the acyl ligands within these complexes should be viewed as lying somewhere between anionic umpolung acyl and oxo-carbene. However, reactions of the acyl complexes with a variety of organic electrophiles did not provide evidence of umpolung acyl reactivity. A number of attempts to prepare alkoxide free magnesium acyls were carried out, and while these were unsuccessful, they did lead to unusual products, the crystallographic and spectroscopic details of which are discussed. Stable s-block acyls: The first isolable s-block metal acyl complexes were readily synthesised through the reductive cleavage of esters using magnesium(I) dimers (see picture). Spectroscopic, crystallographic and computational data suggest that the nature of the bonding within the magnesium-bound acyl fragments lies somewhere between umpolung acyl and oxo-carbene in character.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201703061

You might also like
Never Miss Important Research

Researcher is an app designed by academics, for academics. Create a personalised feed in two minutes.
Choose from over 15,000 academics journals covering ten research areas then let Researcher deliver you papers tailored to your interests each day.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.